Lubrication



can Au 12, 1941 PATENT OFFICE wmuoarron Carl F. Prutton, ClevelandHeights, Ohio, assignor to The Lubri-Zol Corporation, Clevelan Ohio, acorporation of Ohio No'Drawing.

Application March 23, 1938, Serial No. 197,734

9 Claims. (Cl.252-54) I This invention relates as indicated tolubrication, and more particularly to an improved composition of matterwhich may be employed as an addition agent to lubricating compositionsgenerally, (1) for tht purpose of imparting thereto certain desirablecharacteristics such as (a) the ability to maintain lubrication underconditions of extreme pressure and (b) resistance to oxidation and theformation of sludge; and/or (2) the ability to impart (a) improvedlubricating properties to lubricating compositions, while at the sametime, (b) reducing the corrosive effect of the lubricant upon thebearings and associated metallic parts.

By extreme pressures" are meant pressures of" or substantially in excessof 10,000 lbs. per square inch, such pressures now being commonlyencountered in hypoid gears, bearings, contact surfaces of cylinders andpiston rings in internal combustion engines, and many other points. Suchpressures between rubbing surfaces are beingencountered with increasingfrequency as the arts progress.

It is, therefore, the principal object of my invention to provide anaddition agent for lubricating compositions which will improve thelubricating properties of such compositions with respect to one or moreof theabove-named desirable characteristics. Other objects of myinvention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention,then, consists of the means hereinafter fully described, and particu--larly pointed out inthe claims, the following description setting forthin detail certain approved combinations of ingredients embodying myinvention, such disclosed means constituting, however, but certain ofvarious forms in which the principle of the invention may be used.

Broadly stated, this invention comprises the provision of additionagents for use in lubricating compositions, which addition agents may bedescribed as reaction products of complex organic oils, fats, or waxes.with a phosphorusand halogen-containing reagent.

In the foregoing definition of the generic invention there has beenemployed the term complex organic oils, fats, or waxes. By this term. asused in the specification and in the claims, is meant that general classof products of which the specific examples hereinafter given arerepresentative.

Inasmuch as the addition agents provided by this invention for use inlubricating compositions may be very conveniently and correctlydescribed by having reference to their mode of preparation, 1. e., thematerials used in the reactions producing the addition agents, it isbelieved that the following classification of the reaction materialswill describe the addition agents with suflici'ent accuracy.

The complex organic oils, fats and waxes which may be used in thepreparation of addition agents contemplated by this invention may beclassified as follows:

other method, as for example,

Alox. (Burwell pat.)

The phosphorusand halogen-containing reagents contemplated for use in myinvention in providing theimproved addition agents may be classifiedfrom the standpoint of the desirability of the products produced therebyaccording to the valency of the phosphorus, viz:

I. Valency of phosphorus three or less:

Phosphorus chloride P2014 Phosphorus tpichloride; POI: Phosphorustribromide PBrs Phosphorus tri-iodine PI: Phosphorous oxy-chloride POCIPhosphorous sulpho-chloride PSCI Halogen derivatives of phosphine andorganic substituted phenyl chloride, (Cal-Ts) PO12 II. valency ofphosphorus more than three:

Phosphorus pentachloride PCls Phosphorus dichlor-trifluo- PClzF:

ride Phosphorus trioxy-tetra- P203014 chloride Phosphorus oiwchloridePOCla Phosphorus oxybromide POBra Phosphorus thiochloride PSChPhosphorus thiobromide PSBrz Phosphorus thiobromide PaSsBn Phosphorusiodochloride P1201; Phosphenyl oxychloride (CoHs) OPClz f the improvedaddition agents provided by this invention, those formed from oils,fats, or waxes of mineral origin are usually to be preferred for thereason that the addition agents resulting therefrom are generally moreresistant to oxidation and sludge-forming tendencies than those producedfrom oils, fats, or waxes of non-mineral origin.

The addition agents produced by reactions with reagents of the group inwhich the phosphorus has a valency of three or less are usuallypreferred for the reason that such addition agents, in general, producedesirable combinations of characteristics in the lubricant to which theyare added in that the resulting lubricant is simultaneously particularlyresistant to oxidation, as well as having a less corrosive eilect onmetallic bearings and associated parts as compared with the untreatedlubricant.

A preferred class of addition agents for use in phosphines, e. g.phoswhich oxidation or corrosion-inhibiting is of especial importanceare reaction of oils or waxes a reagent in which the phosphorus has avalenc: of three or less for the reasons indicated above As a specificexample of this last class of preferred addition agents, the followingmay be mentioned:

The product produced by reacting a reflnec' mineral lubricating oil,preferably of Pennsylvania origin with phosphorus trichloride.

The procedure in producing such product is as follows:

In general, the reaction is carried out by adding to the complex organicoil, fat, or wax, hereinafter for convenience referred to as a complexoil, a minor proportion of the phosphorus and halogen-containingreagent. The exact proportion of the reagent will depend upon the natureof the oil and the reagent, in most cases being on the order of 5 to 30%by weight and preferably of a sufficient amount so that an excess willbe present, as indicated by the presence of untreated reagent at the endof the reaction those produced by th of mineral origin witl period.

The mixture is heated to a temperature of about C., the exacttemperature depending upon the boiling point of the reacting materialswhich, in the case of volatile materials, may make it necessary to heatunder pressure. In most cases, atmospheric pressure may be employed andthe reaction vessel provided with a reflux condenser to prevent loss ofthe reacting materials during the heating period.

In the case of certain of the less reactive :reagents highertemperatures may be required to cause the desired reaction, for example,as high as C. or even 200 C. or more.

may be preferred to carry out the reaction in the vapor phase as, forexample, by volatllizing the materials to be reacted and passing themixed vapors through heated tubes or causing reaction to take place bymeans of other types of equipment or methods of promoting reaction.

The reaction period is preferably continued for about 1 to 10 hours; inmost cases, three hours being a suilicient length of time. At the end ofthe reaction period, the product may be washed with water to decomposeand remove the excess reagent, or it may be desirable to wash withsolutions of alkalies or to treat with solid alkaline materials,especially where the reagent is of a more stable type.

After removal of the excess reagent, it is usually desirable to removefrom the material such unstable or easily decomposed products as arestill present. This may advantageously be done by blowing with steam, ortreating with solutions of alkalies, or by heating with solid alkaliar:materials to a temperature of from 100 to The following example is givenby way of illustration, only:

A Penna. bright stock is treated with about 20% by weight of phosphorustrichloride PCla, the mixture heated to boiling in a glass, orglasslined, vessel provided with a reflux condenser, for about threehours. The product is washed with water and then blown with steam forabout 1 one-half hour and finally diluted with benzene to facilitateseparation from the water layer; the benzene layer is then separated andthe bellzene removed by distillation, leaving the final product-as theresidue. The appearance and physical characteristics of the product thusobtained are quite similar to that of the original bright stock. Ananalysis showed a chlorine content in-the product of about 0.7%.

Another addition agent was prepared in. exactly the same manner as abovedescribed using planation, it is believed that the workers in the artwill be able to determine very readily the particular concentrationswhich produce the 1% of the addition agent produced, as previouslyexplained, from Penna. bright stock or neutral oil, caused a very markedreduction in the corrosion of cadmium silver and lead bronze bear- 5ings exposed to a Penna. S. A. E. motor oil a Penna. neutral oil insteadof a Penna. bright for a period of 192 hours at a temperature of stockand the two resultant products were sub- 150 C. stantially equivalent intheir physical charaoter- While it is believed that the film strengthimistics and general effectiveness as addition proving eflect of theaddition agents of this ina ts- 10 vention may be due to a chemical or P37 100- Other addition agents were prepared by treatchemical action uponthe metallic surface under ing the following in a similar way withphosconditions of extreme pressure, it is to be unphorus trichloride:dertsood that this invention is not intended to be limited by anyexplanation or theory. The 8133 222 2 2322 35 15 corrosion-inhibitingeffect may be obtained ei- Furfuml extract of mineral oil ther byprotective action on the metal surfaces u gas on or a catalytic effectof the phosphorus in the composition, or the addition agent may reactThe addition agents contemplated for use in with the oil to render itrelatively non-corrosive. this invention may be added to anyconventional The precise action is not known. lubricating oil, such asmineral 011 (more spe- The following tables give the results ofcerciflcally, motor oils), and may be employed in tain corrosion testson diil'erent bearing alloys various combined oils so long as theremaining by the base oil and the same oil to which has constituents arenot incompatible with the adbeen added different addition agentsprepared dition-agents herein defined. The concentration as aboveexplained.

of addition agents found most useful in mineral lubricating oils willvary, for example, becon-0mm test 192 hours at tween about of 1% up to2%; however, higher 011 Percent change in concentrations up to 20% maybe employed for weight particular uses. gg g gf The presence of thenamed addition agents Type S.A.-E 53; Lead Babin substantial proportionsin lubricating comsilver hm positions generally, will usually improvecertain properties such as the extreme pressure char- 10 None -o. 12 0.51 0.00 acteristics of the composition, even though the flagg3 additionagent may be present over a wide range I 1 Neut.-PCl3.:: I ofconcentrations. Corrosion tests on lubricants i E igggqg containingvarious concentrations of certain of Pennsylvania the addition agentshave shown, however, that 4 g ggggjggg for certain types ofoil a lowconcentration, 40 413i. St.-PCl;

i. e., on the order of one-half percent or less, e i if gif;

will markedly improve the corrosion character- Non e istics of thelubricant; whereas, concentrations M16430; figggigggfi of 1% effect noimprovement and may, in innent. 30 -%Br.-St.PC1-

stances, increase the corrosiveness of the com- 23111:: i if'fi jj gjjposition. In the case of other addition agents or other base oilsconcentrations of may It will be noted from the above table that have nomarked influence on the corrosion facwhen the correct percentages ofaddition agent tor; whereas, concentrations of 1% have been areemployed, the loss of weight of the bearings found to materially improvethe corrosive tendis as little or even less than when the untreatedencies of the oil. In determining the concentraoils are used.

tlons which will produce the best results, tests The following tableindicates the results of may advantageously be conducted with theparcertain well-known tests designed to show the ticular base oil towhich the addition agents are condition of the oils at intervals duringtheir to be added; however, with the foregoing exuse. It will be seentherefrom that the oils to which the addition agent has been added showmarked improvements over the ordinary lubricating oils and a generalresistance to deteriorabest results. For-example, I have found thattion. Indiana oxidation tests Type Penrn- PenrL-- Penn --{%A.E Non t610811 0H8- Inhlblt" Agent Noneut-P015-.. at. strata- OonradsonOriginal"--- 0.18.-- 0.14 0.18

car n. hours-. 1.78.-. 0.89 0.77 Viscoslty 0riginal 46.3.-- 47.0 46.9.-

100 hours-.-- 52.9--. 43.3 4.8.9 Percent in- 14.2-.- 3.8 4.2 S.U.S.at210crease in F. viscosity at 100 H hours. 1

OIIIS 1'6- quimq 1 10 mgs 32.5... 87.0 82.5 M rg than M o ra than 1 5than gg g 100mgs 96.0-.- Morethanlfifl. Morethanl50.

'Neut.-PCI;=Pennsylvanla -neu treated with phosphorus trichloride.

.Br. St.-POh=Pennsylvania bright stock treated with phosphorustrichloride.

"Indiana oxidation tests T Mid-continent Mid-continent Mid-continentMid-continent. OiL ?1%No- $1110 2 30 so.

- ercen one l Agent None. Neut.-Pl; n St.-PC1.1 B2". Sit-PO13. Oonradson{O 0 0. 0.49.-. 0.47.

carhpn. 100 urs 2 1.26. Viseosrty---.. 0r 63.7. 100 ours--- 68.7. S. atPercent in- 7.8.

0 F. crease in viscosity atl00hours. Hours re quired for mgs 39.5..07.0.- 76.0 Approx. 170. pizeclfpital00mgs 97.0 145.0.-. 760.... Approx.170.

Nore.-Test was continued until amount of precipitate was at less in 150hours or less. Otherwise test was discontinued at 150 hours.

The following is a description of an example illustrating the type oflubricating composition included in the present invention.

Fifty-five pounds of Pennsylvania Bright Stock were placed in an' ironreactor equipped with a suitable heating device, agitator, cover, andreflux condenser. chloride were added and heated to 180 C., andmaintained at that temperature for about 1% hours. The contents of thereactor were then cooled, transferred to a wooden tank, and diluted withabout 7 gallons of benzol. About 7 gallons of water were placed in thesame tank and the two layers thoroughly agitated together. The water wasthen allowed to settle and the water layer drawn off from the bottom ofthe tank. The water wash operation was repeated, and 1% hours allowedfor separation of the water layer before removing.

Low pressure steam was blown through the remaining product for twohours, after which the product was allowed to stand for about 48 hoursto efi'ect complete separation of the entrained water.

The benzol solution was then transferred to a glass-lined vacuum stilland the benzol removed by distillation under a vacuum equivalent to 27"of mercury. The distillation was discontinued when the temperatureof'the liquid in the still reached 110 C.

The product thus obtained had the following characteristics:

Per cent free HC] 0 Per cent ash .10 Per cent chlorine 1 .023 Per centphosphorus .046 Vis. at 210 F. in S. U. S 148 product was.found tmbe avery effective oxidation inhibitor when incorporated, in an amount ofabout 1% or less. in various types of mineral lubricating oil. Theoxidation inhibiting effect of this product was tested by means of amodified Indiana oxidation test in which the conditions were, ingeneral, the same as those previously described for the Indianaoxidation test, with the exception that a coil consisting of 9 feet of18 gauge iron wire, polished with emery cloth, was placed in theoxidation tube entirely submerged in the oil sample.

The results obtained with this test on three different types of oil, andthe same oils containing 1% of the product prepared according to theabove description, are shown in the following table:

1.1 pounds of phosphorus tri-.

t 100 mg. in case this amount was precipitated Pennsylvania PennsylvaniaMid-continent SAE 10 SAE 40 SAE 30 motor oil motor oil motor oil No +1%No .5% No .s% addiinhibaddiinhibaddiinhibtlon itor tion itor tion itorCONTINENTAL OXIDATION Conradson carbon:

Original..... .19 .15 1.30 1.01 .34 .11 At 48 hours. 3. 05 75 2. 58 l.49 2. 32 l. 26 Saybolt vis. at

Original" 46. 5 46. 7 82. 9 83. 9 63. 5 64. 0 All 48 hours. 64. 8 48. 693. 9 86. 6 81.5 72. 4 Percent vis. inc. at 48 hours 39.3 4.0 13. 05 3.0 28. 4 13.0 Naphtha insol.

Hrs. for 10 22.5 42.0 14.5 33.0 Hrs. for 100 mgs 40.5 32.5 Mgs. at 48hrs 217. 0 14. 8 4.0 8. 2 210 44. 9 Acid number 01'iginal .17 .08 .04.11 .08 At 48 hours. 2. 23 .81 1. 26 37 1.38 73 SHELL CORROSION Percentchange in weight:

Lead-bronze. 1. .07 l0 10 15 l0 Babbitt-.. 18 .05 0 .0l 0 04 Other modesof applying the principle of my invention. may be employed instead ofthe one explained, change being made as regards the materials employedin carrying out the process provided the ingredient or ingredientsstated in any of the following claims or the equivalent of such statedingredient or ingredients be employed.

I, therefore, particularly point out and distinctly claim as myinvention:

1. A lubricating composition comprising a mineral lubricating oil withthe properties of such composition affecting its use as a, lubricantimproved by incorporating therein from an effective amount to about 20%,based on the amount of mineral oil, of a composition selected from thefollowing class;-the reaction product of a complex organic wax ofmineral origin and a phosphorus-and-halogen-containing reagent in whichthe phosphorus has a valence of three or less; the reaction product of acomplex organic oil of mineral origin and aphosphorusand-halogen-containing reagent in which the phosphorus has avalence of three or less; the total amount of phosphorus in thelubricating composition being less than {6% thereof.

2. An addition agent for lubricating compositions, comprising thereaction product of complex organic oil oi mineral origin with aphosphorus-and-halogen-containing reagent in which the phosphorus has avalence of three or less, such product containing less than 6% ofphosphorus.

3. An addition agent for lubricating compositions comprising thereaction product of a complex organic wax of mineral origin with aphosphorus-and-halogen-containing reagent in which the phosphorus has avalence of three or less, such. reaction product containing less than 16% phosphorus.

4. A lubricating composition comprising a mineral lubricating oil withthe properties of such composition affecting its use as a lubricantimproved by incorporating therein from an eflective amount to about 20%,based on the amount of mineral oil, of the reaction product of a complexorganic oil of mineral origin and a phosphorus-ancl-halogen-containingreagent in which the phosphorus has a valence of three or less,

said reaction product containing less than {6%- phosphorus.

5. A lubricating composition comprising a mineral lubricating oil withthe properties of such composition affecting its use as a lubricantimproved by incorporating therein from an effective amount to about 20%,based on the amount oi mineral oil, of the reaction product of a complexorganic wax of mineral origin and a phosphorus-and-halogen-containingreagent in which the phosphorus has a; valence of three or less. saidreaction product containing less than 155% phosphorus.

6. A lubricating composition comprising a mineral lubricating oil withthe properties of such composition aiIectinB its use as a lubricantimproved by incorporating therein from about 0.1% to about 2%. based onthe amount 01 mineral oil, or the reaction product or a complex organicoil of mineral origin and a phosphorusand-halogen-containing reagent inwhich the phosphorus has a valence of three or less, said reactionproduct containing less than 1 6% phosphorus. r

'1. An addition agent for lubricating compositions comprising thereaction product of a complex organic oil of mineral origin with aphosphorus-and-chlorine-containing reagent in which the phosphorus has avalence of three or less. the total phosphorus content of suchreactionproduct being less than 8. An addition agent for lubricatingcompositions comprising the reaction product of mineral oil with aphosphorus-and-halogen-containing reagent in which the phosphorus has avalence of three or less, said reaction product having a phosphoruscontent of less than .05%

9. A lubricating composition comprising a mineral lubricating oil withthe ability of such composition to resist oxidation improved byincorporatingtherein a small amount. based on the amount of mineral oil,of the reaction product 01 a complex organic oil of mineral origin witha phosphorus-and-chlorine-containing reagent in which the phosphorus hasa valence or three or less, said reaction product containin less thanabout .05% phosphorus.

CARL F. PRUTI'ON.

